You definitely cannot assume that: Windows could be installed on a different drive letter, or in a different directory. On a previous work PC Windows was installed in D:\WINNT, for example.
The short answer is to use the API call GetSystemDirectory(), which will return the path you are after.
The longer answer is to ask: do you really need to know this? If you're using it to copy files into the Windows directory, I'd suggest you ask if you really want to do this. Copying into the Windows directory is not encouraged, as you can mess up other applications very easily. If you're using the path to find DLLs, why not just rely on the OS to find the appropriate one without giving a path? If you're digging into bits of the OS files, consider: is that going to work in future? In general it's better to not explicitly poke around in the Windows directory if you want your program to work on future Windows versions.